Chemiluminescent smokes

ABSTRACT

A METHOD OF ILLUMINATING AN AREA USING A CHEMILUMINESCENT SMOKE COMPOSITION CONTAINING AN ALUMINUM ALKYL COMPLEXED WITH AN AMINE OR AN ETHER AND THEN MIXED WITH A CHEMILUMINESCENT AGENT. FOR EXAMPLE, TRIETHYLALUMINUM COMPLEX WITH A HEXAMETHYLENE TETRAMINE OR DIETHYLETHER AND MIXED WITH A CHEMILUMINSCENT AGENT, SUCH AS TETRAKIS DIMETHYLAMINO ETHYLENE, WHEN CONTACTED WITH WATER PRODUCES A CHEMILUMINESCENT SMOKE OF SUFFICENT INTENSITY TO LIGHT AN AREA.

United States Patent 3,679,594 CHEMILUMINESCENT-SMOKES Urho A. Lehikoinen, Detroit, Mich., assignor to Ethyl Corporation, New York, N.Y.

N 0 Drawing. Continuation-impart of applications Ser. No. 561,337, June 29, 1966, now Patent No. 3,496,111, Ser. No. 649,820, now Patent No. 3,576,752, Ser. No. 649,821,now Patent No. 3,551,341, Ser. No. 649,835, now Patent No. 3,551,342, Ser. No. 649,836, now Patent No. 3,576,753, Ser. No. 649,838, nowPatent No.

, 3,576,754, and Ser. No. 649,850, all June 29, 1967, and application Ser. No. 778,316, Nov. 22, 1968, now Patent No. 3,551,343, which is a continuation-in-part of application Ser. No. 561,418, June 29, 1966. This application Dec. 18, 1969, Ser. No. 886,349 The portion of the term of the patent subsequent to Feb. 17, 1987, has been disclaimed Int. Cl. C06d 1/10; C09k 3/00 U.S. Cl. 252-1883 25 Claims ABSTRACT 'OF THE DISCLOSURE A method of illuminating an area using a chemiluminescent smoke composition containing an aluminum alkyl complexed with an amine or an ether and then mixed with a chemiluminescent agent. For example, triethylaluminum complexed with a hexamethylene tetramine or diethylether. and mixed with a chemiluminescent agent, such as tetrakis dimethylamino ethylene, when contacted with water produces a chemiluminescent smoke of suflicent intensity to light an area.

CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of my copending applications Ser. No. 561,337, filed June 29, 1966, now U.S. Pat. 3,496,111.; Ser. Nos. 649,820; 649,821; 649,835; 649,836; and 649,838, filed June 29, 1967, now U.S. Pats. 3,576,752; 3,551,341; 3,551,342; 3,576,753; and 3,576,754, respectively; Ser. No. 649,850, filed June 29, 1967; and application Ser. No. 778,316, filed Nov.

22, 1968, now U.S. Pat. 3,551,343, which in turn is a continuation-in-part of application Ser. No. 561,418, filed June 29, 1966, now abandoned.

BACKGROUND OF THE INVENTION (1) Field of the invention This invention relates to the illumination of an area by generating a light-producing smoke in the area to be illuminated. Generally, the invention utilizes an organometallic smoke formulation which includes an agent capable of producing light by chemical means. More specifically, the invention is a method of illuminating an area by generating an organoaluminum-based chemiluminescent smoke.

(2) Description of the prior art 3,679,594 Patented July 25, 1972 at the locus of use. In U.S. 3,309,268 and U.S. 3,400,- 082, smoke formulations are described containing alkyl aluminum smoke agents. The smoke formulations provided by this invention do not depend solely upon a reaction with atmospheric moisture but rather, to a large extent, upon the presence of water. Furthermore, the smoke agents described herein produce a smoke which glows and in this it is unique among all prior art smoke agents.

In the aforementioned copending parent applications, I have disclosed chemiluminescent smoke agents which have properties superior to the conventional smoke agents. In addition, the chemiluminescent smoke agents fulfill a duel purpose role since they are capable of use both by day and at night.

SUMMARY OF THE INVENTION The invention is a method for illuminating an area by generating a chemiluminescent smoke in said area. The light resulting from the release of said chemiluminescent smoke permits not only the smoke itself to be seen, but provides sufficient illumination to enable the surrounding area to be seen. Thus, it is an object of the present invention to provide a smoke with sutlicient luminous intensity to light an area at night. A further object is to provide a smoke composition which is non-hazardous, non-toxic, for use by dayand night. A further object is to provide a method of producing a smoke composition useful as a marking, signalling, and illuminating means.

These and other objects can be accomplished by providing a method for illuminating an area comprising generating a chemiluminescent smoke in the area. The smoke generation is produced by contacting water with a chemiluminescent smoke agent consisting essentially of an aluminum alkyl component, a complexing agent (e.g., an amine or an ether), and a chemiluminescent agent such as a tetrakis(alkylamino)ethylene, a nitrile, a porphine, an indole, a pyrrole, an imidazole, or an acridine.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The method of illuminating an area comprises generating a chemiluminescent smoke of sufiicient luminous intensity to allow the area to be seen at night. The chemiluminescent smoke is produced by contacting with water a chemiluminescent smoke agent consisting essentially of (a) An aluminum alkyl selected from trialkyl aluminum, dialkyl aluminum hydride, and mixtures of these, said aluminum alkyl having the formula:

ERR'R"Al wherein R and R are alkyl radicals of 1-4 carbon atoms and R" is hydrogen or an alkyl radical of l-4 carbon atoms, said aluminum alkyl being complexed with a chemically equivalent amount of (b) A complexing agent wherein said complexing agent is an alkyl amine having up to six carbon atoms or an ether having up to about 15 carbon atoms and l-3 etheroxygen linkages, said ether being free of acetylenic bonds, and admixed with (c) A chemiluminescent agent wherein said chemiluminescent agent is selected from the group consisting of (i) a tetrakis(di-lower alkylamino)ethylene, wherein said lower alkyl is a hydrocarbyl group having up to about 4 carbon atoms;

(ii) a hydrocarbyl-substituted nitrile, wherein said hydrocarbyl group is an alkyl, aryl, aralkyl, or alkaryl group having up to about 12 carbon atoms;

(iii) a porphine selected from the group consisting of porphine, alkyl-substituted porphines, and metal chelate derivatives thereof wherein said alkyl substituent has up to fiive carbon atoms and said metal chelate derivatives are formed from metals selected from Groups IB,

II-A, II-BIIII-A, and transition metals;

(iv) an indole selected from the group consisting of indole and hydrocarbyl-substituted indoles wherein said hydrocarbyl substituent is an alkyl, aryl, 'alkaryl, or aralkyl group having up to about 12 carbon atoms;

(v) a pyrrole selected from the group consisting of pyrrole and hydrocarbyl-substituted pyrroles wherein said hydrocarbyl substituent is an alkyl, aryl, aralkyl, or alkaryl group having up to about 12 carbon atoms;

(vi) a hydrocarbyl substituted imidazole wherein said hydroc'arbyl-substituent is an alkyl, aryl, alkaryl, or aralkyl group having up to about 12 carbon atoms, and

(vii) an acridine being selected from acridine and hydrocarbyl-substituted acridines wherein said hydrocarbylsubstituent is an alkyl, aryl, alkaryl or aralkyl group having up to about 12 carbon atoms.

These compositions yield chemiluminescent smoke clouds when admixed with water, The method of water mixing is notJcritical. The smoke agent may be injected underneath the surface of water to yield a cloud of chemiluminescent smoke above the surface of the water. Alternatively, the smoke agent can be merely admixed with water by shaking the agent and water in a vessel. Another method for contacting the agent with water is to introduce a stream of the agent into a water spray. Moreover, the water may be atmospheric, the smoke agents of this invention are sensitive to high humidity.

One essential ingredient in the smoke compositions of this invention is an aluminum compound of the types given above. Preferably, all alkyl radicals bonded to the aluminum atom are identical. Most preferably, these alkyl radicals are solely composed of carbon and hydrogen and have up to 4 carbon atoms. Typical examples of alkyl aluminums which are applicable in this invention are trimethyl aluminum, triethyl aluminum, diethylaluminum hydride, methyl diethyl aluminum, triisopropyl aluminum, tri-sec-butyl aluminum, triisobutyl aluminum, and the like.

Highly preferred organoaluminum compounds employed in this invention include tri-n-propylaluminum, tri-n-butylaluminum triisobutylaluminum, tri-n-amylaluminum, tri-sec-amylaluminum, tri-n-hexylaluminum, triphenylaluminum, ethyldiphenylaluminum, and the like, and mixtures thereof. A most highly preferred aluminum alkyl is triethylaluminum.

Highly preferred organoaluminum hydrides employed in this invention are diethylaluminum hydride, dimethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, diisobutylaluminum hydride, ethylmethylaluminum hydride, ethyl-n-propylaluminum hydride, isopropylisobutylalumiuum hydride, and the like, and mixtures thereof.

All the organic radicals bonded to the metal atom or atoms (in the organometallic compounds employed in this invention) need not be identical. "For example, two or three different radicals can be bonded to aluminum. Compounds of this type are illustrated by dimethyl ethyl aluminum, diethyl methyl aluminum, methyl diisopropyl aluminum, methyl hexyl butyl aluminum, and the like. Thus, the organoaluminum compounds applicable in this invention include compounds having the formula RR'R"Al wherein R, R and R" are hydrogen or an alkyl radical of one to six carbon atoms. Highly preferred triorganoaluminum compounds are those wherein R, R are alike or different alkyl radicals of one to four carbon atoms, and R is hydrogen or an alkyl radical containing one to four carbon atoms.

Whenever a triorganoaluminum compound is mixed with a diorganoaluminum hydride, the resulting composition does not remain merely as a physical mixture of two specific compounds. Under such conditions, molecular rearrangement or disproportionation takes place. Thus, the organic and the hydrogen radicals exchange until an equilibrium is obtained. The end result is that the composi- 4 t tion is not merely a mixture of two compounds, but a mixture of many compounds containingcompositions .intermediate between the two original compounds.

The operation of disproportionation may be illustrated by the following example. If originally triethylaluminum, triisobutylaluminum and diethylaluminum hydride are mixed, the resulting disproportionation product will contain the following intermediate compounds: diethylisobutylaluminum, ethylisobutylaluminum hydride, ethyldiisobutylaluminum, and diisobutylaluminum hydride. Similar disproportionation takes place when mixtures of triorganoboron and diorganoboron hydride are employed.

For the purposes of this invention, the aluminum alkyl is complexed with an amine or an ether. A wide variety of amines can be employed. The exact nature of the amine is not critical, provided it can complex with the aluminum compound and is devoid of substituent groups which lead to deleterious side effects. Preferably, the amines are selected from hexamethylenetetramine and tetralower-alkyl ethylene diamines. (For the purpose of this invention, lower alkyl signifies alkyl radicals of one to four carbons.) V

A wide variety of tertiary and hindered secondary amines can be employed. 'Any tertiary amine may be employed, but for practical reasons, tertiary amines having up to about 15 carbon atoms are preferred. Illustrative examples of applicable amines are N,N-dimethylaniline, dicyclohexylamine, N-benzyl-N-ethylaniline, N-benzyl-N- ethyl-m-toluidine, dibenzylamine, ditolylamine, diisobutylamine, tert-butylamine, N,N-diethylaniline, tribenzylamine, tri-n-octylamine, triphenylamine, N,N-dimethyl benzylamine, dodecyldimethylamine, N,N-di-me'thyl-O, m-, and p-toluidines, N,N-diethyl-o-, m, and p-toluidines, N,N-ethylmethylaniline and the like.

Highly preferred amines are alkyl amines having up to about six carbon atoms. Examples are methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-butylamine, ethyl-n-butylamine, isopentylamine, n-hexylamine, and the like. Most preferably, the amines are selected from hexamethylenetetramine and tetra(lower alkyl)diamines and hexa(lower alkyl) diamines such as tetramethylenediamine, tetraethylenediamine, tetrapropylenediamine, tetrabutylenediamine, hexamethylenediamine, hexaethylenediamine, hexapropylenediamine, hexabutenediamine, and the like.

For the purposes of this invention, the aluminum alkyl can be complexed with an ether instead of an amine. A wide variety of ethers can be employed. The exact nature of the ether is not critical provided it is devoid of substituent groups which lead to deleterious side effects. Preferably, the ethers have up to about 15 carbon atoms. They may have one, two, or three or more ether linkages, -O-- but preferably contain 1-3 ether-oxygen linkages. More preferably, the ethers employed in this invention are free from acetylenic linkages.

Monoethers which may be employed have the formula:

wherein R and R are independently selected from alkyl groups having 1 to 4 carbon atoms; aryl groups such as phenyl and tolyl; alkenyl groups of 3-5 carbon atoms such as allyl; cycloalkyl groups such as cyclohexyl, and the like. Typically preferred ethers of this type are diethyl ether, isopropyl ether, allyl ether, phenyl ether, anisole, benzyl ether, benzyl ethyl ether, m-methylbenzy'l. ether, and the like. Cyclic monoethers can be employed such as tetrahydrofuran. A highly preferred ether which is used in this invention is tetrahydrofuran. Biethers, that is, ethers which contain'two ether-oxygen linkages, can be employed in this invention. Typical ethers of this type which may be employed are ethyleneglycol dimethylether, ethyleneglycol diethyl ether, ethyleneglycol, dibutylether; ethyleneglycol diamylether, dioxane, and the like.

Triethers (sometimes referred to as tridentate ethers) which may be employed in this invention preferably have the ether-oxygen linkages separated by two carbon atoms; that is, ethylene radicals. Typical ethers of this type which can be employed in this invention are diethyleneglycol dimethylether, diethyleneglycol diethylether, diethylene glycol dibutylether, and hexylamylether of diethyleneglycol.

The complexing of the alkyl aluminum with the amine or ether is conveniently carried out by simply mixing the alkyl aluminum and the complexing agent, that is, either the amine or ether under anhydrous conditions and in the presence of an inert atmosphere. Typically, nitrogen is used to provide the inert atmosphere. However, the other inert gases, such as argon and neon can be employed, if desired. Best results are obtained when all of the alkyl aluminum is complexed with the amine or ether. Thus,

when a monoamine or monoether is used as the complexing agent, at least one mole of the amine or ether is employed for each mole of alkyl aluminum. Similarly, when using a diamine or diether, at least one-half mole of amine or ether is employed for each mole of alkyl aluminum. Furthermore, when a triether is employed as the complexing agent, at least one-third mole of the ether is complexed to each mole of alkyl aluminum. Also, when a tetramine is employed, at least one-quarter mole of the tetramine is used for complexing to each mole of alkyl aluminum. Depending on the complexing agent employed, a mole ratio of from 1:5 to 4:1 of alkylalumimum to complexing agent is preferred. Thus, it is not necessary to employ an exactly chemiequivalent amount of ether or amine and alkylaluminum. An excess of the complexing agent can be used beneficially since it appears that the presence of excess complexing agent produces larger smoke clouds. Consequently, it is convenient to employ up to five equivalents of ether or amine complexing agent for each equivalent of alkylaluminum.

After the alkylaluminum component is complexed with the amine or the ether, it is then mixed with an amount of the chemiluminescent agent which is sufficient to yield a chemiluminescent smoke of desired illumination capacity. Thus, the amount of chemiluminescent agent preferably employed is sufiicient to yield a final preparation containing from 20 to 50 weight percent of the chemiluminescent agent. A highly preferred chemiluminescent smoke is produced by a formulation containing from 30 to 50 weight percent of the chemiluminescent agent. A most preferred final preparation contains 40 weight percent of the chemiluminescent agent. It should be understood that the above are practical formulations only and no criticality is found in the particular ranges of chemiluminescent agents disclosed. The only requirement as to the amount of chemiluminescent agent is that a sufficient amount be included to yield a final preparation which will generate a sufficient amount of light to illuminate the desired area.

The amount of aluminum alkyl can vary from 50 to about 80 percent by weight of the total chemiluminescent smoke composition. Preferred ranges of aluminum alkyl are from 50 to 70 percent by weight. Highly preferred smoke compositions contain about 50 to 60 percent by weight of aluminum alkyl.

Many chemiluminescent materials are known and can be used in this invention. The only requirements of such chemiluminescent materials is that they be compatible with the other ingredients of the smoke agent and not add reaction products deleterious to personnel or container: materials. Among the chemiluminescent materials found preferred for the composition of smoke are tetrakis(dilower alkylamino)ethylene, nitriles, porphines, pyrroles, indoles, imidazoles, and acridines.

The tetrakis(di-lower alkyl amino)ethylene can be any such compound in which the lower alkyl portion has up to about four carbon atoms. Preferred embodiments of lower alkyl groups are methyl, ethyl, propyl, and butyl groups. Highly'preferred embodiments of the tetrakis compounds are tetrakis(dimethylamino)ethylene and tetrakis(dibutylamino)ethylene.

Another suitable chemiluminescent ingredient in the compositions of this invention is a hydrocarbyl-substituted nitrile. By hydrocarbyl is meant a moiety containing only hydrogen and carbon atoms. Any alkyl, aryl, aralkyl, or alkaryl containing-nitrile may be employed, but for practical reasons, nitriles having up to about 16 carbon atoms are preferred. lllustrative examples of nitriles useful in this invention are acrylonitrile, acetonitrile, propionitrile, butyronitrile, 3,B-dimethylbutyronitrile, Z-ethylhexylnitrile, heptanenitrile, B-methylheptanenitrile, dodecylnitrile, tridecanenitrile, n-pentadecylnitrile, benzonitrile, cycloheptanecarbonitrile, 4-cyclohexylbutyronitrile, cyclohexylphenylacetonitrile, cyclopentylacetonitrile, cyclopropanecarbonitrile, 1,2-cyclobutanedicarbonitrile, 2,3-diphenylsuccinonitrile, 1 ,'6-hexanedicarb onitrile, diphenylacetonitrile, 2,2-diphenylpropionitrile, heptadecanenitrile, isobutyronitrile, Z-phenylpropionitrile, o, m, and p-tolylacetonitrile, (o-ethylph enyl) acetonitrile, (p-isopropylphenyl acetonitrile, l-naphthylacetonitrile, o, m, and p-phenylenediacetonitrile, o-tolunitrile, 2,Z-dimethylpropionitrile, naphthonitrile, phenylnitrile, wnaphthylnitrile, fi-naphthylnitrile, 7-indenyl nitrile, 6-isoindenylnitrile, S-acenaphthylnitrile, l-fluorenyl nitrile, a-cyanoanthracene, 3-cyanophenanthrene, benzylnitrile, a-methylbenzylnitrile, a,a-dimethylbenzylnitrile, 4-hexyl-a,a-dimethylbenzylnitrile, 4-methylphenylnitrile, 4-nonylphenylnitrile, 3,S-di-ethylphenylnitrile, and the like Another suitable chemiluminescent ingredient in the composition of this invention is a porphine and its derivatives having the following generic formula:

Preferred porphines are those selected from the groups consisting of porphine, alkyl-substituted porphines in which the alkyl radicals have up to five carbon atoms and metal chelate derivatives thereof in which the metal is selected from Groups I-B, H-A, II-B, III-A and the transition metals. Illustrative examples of porphines useful in this invention are porphine, alkyl-substituted porphines such as ZO-methylporphine, 5,9,14,20 tetraethylporphine, 4,14-dipentylporphine, as well as metal chelates of Groups I-B, II-A, II-B, III-A and transition metals. Specific examples of metals which form chelates are copper, iron, cobalt, manganese, calcium, magnesium, nickel, and the like. Examples of such metal chelates are copper porphine, silver porphine, zinc porphine, cadmium porphine, mercury porphine, magnesium porphine, calcium porphine, strontium porphine, barium porphine, aluminum porphine, iron porphine, hemin, cobalt porphine, nickel porphine, ruthenium porphine, and the like, including'the alkyl-. substituted porphine chelates of the above.

Another suitable chemiluminescent ingredient in the composition of this invention is an indole selected from indole and hydrocarbyl-substituted indoles having alkyl,

aryl, alkaryl, or aralkyl groups of up to 12 carbon atoms. Illustrative examples of indoles and related compounds useful in this invention are indole,

S-butylindole, 1,2-dimethylindole, 2,5-dimethylindole, 2,7-dipropylindole, 3-hexy1indole, 2,5-dioctylindole, 2,5-didodecylindole, 2,3-diphenylindole 2,5-ditolylindole, 2-methylindole, 3-methylindole,

5 and 7-methylind0le, S-methyI-Z-phenylindole, 2,3,5-trimethylindole, 2-phenylindole, o-pentylphenyl-3-indole, 2,3,7-triethylindole, 2,3,5-tributylindole, 5-ethyl-2-pentylindole, 2,3,5-tridodecylindole, 2-isobutyl-5-phenylindole, 2-phenylethyl-2-indole, 5-phenylhexyl-3-indole, 2-phenylindole, 3 (u-naphthyl)-indole, 4-phenanthryl-indole,3 7-anthracenylindole, a-(4-methylphenyl)-indole, B- (4-hexylphenyl) -indole, 7-benzylindole, 4-(u-methylbenzyD-indole, 4-(4-pentyl-u-methylbenzyl)-indole, and the like.

Another suitable chemiluminescent ingredient in the composition of this invention is a pyrrole selected from pyrrole and hydrocarbyl-substituted pyrroles having alkyl, aryl, alkaryl, or aralkyl groups of up to 12 carbon atoms. Illustrative examples of pyrroles and related compounds useful in this invention are pyrrole, 2,5-dipropylpyrrole, 2-phenylpyrrole, 2-tolylpyrrole, 2,4,5-triethylpyrrole, 2,5 -dibutyl-3 -phenylpyrrole, 2-octylpyrrole, tetraethylpyrrole, tetraphenylpyrrole, l-methylpyrrole, l-isopropylpyrrole, l-pentylpyrrole, l-hexylpyrrole, l-octylpyrrole,

l-decylpyrrole,

l-dodecylpyrrole,

1 -phenylpyrrole,

2,5-diethylpyrroline,

2,5-dibutylpyrroline,

2-phenylpyrroline,

2,3,5-triethylpyrrole,

l-butylpyrroline,

1-ethyl-3-phenylpyrroline,

l-tolylpyrroline,

2,3,4,5-triphenylpyrrole,

2- (p-tert-butylphenyl) pyrrole,

2,5-ditolylpyrrole,

a-(2-phenanthryl)-pyrrole,

B- (a-naphthyl) -pyrrole,

13- anthracentyl -pyrrole,

a- (fluoroenyl) -pyrrole,

a-benzylpyrrole,

cca,a-dimethylbenzyl -pyrrole,

fl- (4-tert-butyl-a-methylbenzyl) -pyrrole,

a-(4-tert-amylphenyl)-pyrrole,

B-(3,5-di-isopropylphenyl)-pyrrole, and the like.

Another suitable chemiluminescent ingredient in the composition of this invention is an imidazole, especially hydrocarbyl-substituted imidazoles in which the hydrocarbyl is an alkyl, aryl, alkaryl, or aralkyl having up to about 12 carbon atoms. Illustrative examples of imidazoles and related compounds useful in this invention are compositions of this invention is acridine and its derivatives having the following structure:

The preferred derivatives are the hydrocarbyl-substituted acridines in which the hydrocarbyl group is an alkyl, aryl, alkaryl, or aralkyl group having up to about 12 carbon atoms. Examplesare l-methylacridine, Z-ethylacridine, l-propylacridine, 9-butylacridine, l-hexylacridine, l-octylacridine, Z-decylacridine, l-dodecylacridine, 9-phenylacridine, 9-( a-naphthyl -acridine, l-benzylacridine,

l-.(4-methylbenzyl) -acridine,

9- (u,u-dimethylbenzyl) -acridine, 1-(4-isopropyl-a,a-dimethylbenzy1)-acridine, 1-(4-ethylphenyl) acridine,

9- 3,5-di-isopropylphenyl) acridine,

and l-tolylacridine.

Illustrative examples of acridines and their derivatives useful in this invention are acridine,

benz[c1acridine, 4-methylacridine, 3,5-dipropylacridine, 4-ethyl-6-hexylacridine, l,4,6,8-tetraethylacridine, and the like.

The mixing of the complex with the chemiluminescent compound is conveniently carried out using simple mixing procedures. As in the case of complexing, a slight amount of heat may be beneficial, that is, it may be desirable to heat up the mixture to a temperature within the range of 30-5 C.

\As pointed out above, the chemiluminescent smoke formulations of this invention yield smoke clouds which are visible at night when admixed with water. The water need not be pure; natural waters such as lake, river, or sea water can be employed as can muddy or wet earth. In addition, the water may be chemically-bound, that is, waters of hydration. When using chemically bound water, a compound which preferentially contains a large amount of waters of hydration is employed. Preferred compounds containing waters of hydration are alums. Typical alums which may be used are described on pages 196-199 of the Eighth Edition of Langes Handbook of Chemistry, Handbook Publishers, Inc., Sandusky, Ohio (1952).

To further illustrate the invention, the following nonlimiting examples are presented. Unless otherwise indicated, all parts are by weight.

EXAMPLE 1 FWt. percent Hexamethylenetetramine 13.8 Triethyl aluminum 45 Tetrakis(dimethylamino)ethylene 39.5 Tetrahydrofuran 1.8

The tetrahydrofuran is not a critical ingredient but aids in the solubilization of the hexamethylenetetramine. Usually about one to three percent of such a solubiliza- 'tion agent is efiicaciously employed. Besides tetrahydrofuran, another typical solubilizing agent that can be used is dioxane. Similarly, many other ethers can be employed.

The resultant smoke formulation yields a chemiluminescent smoke when admixed with water. For example, equal volumes of agent and water when admixed together yield a chemiluminescent smoke. Furthermore, such a smoke is produced when one volume of agent is injected under the surface of approximately 10 volumes of water without artificial stirring. Thirdly, the formulation yields a chemiluminescent smoke when 50 parts of the formulation are added to 100 parts of Similarly, the tetrakis compound may be replaced to yield suitable chemiluminescent smokes by:

tetrakis (dibutylamino) ethylene, benzonitrile,

propionitrile,

a-naphthonitrile,

'2,5-dimethylimidazole,

2-tolylimidazole, acridine, benz[c] acridine, 3-hexylacridine, or S-tolylacridine.

EXAMPLE 2 Following the procedure of Example 1, equimolar amounts of diethylether and triethylaluminum are prepared. To this is added a sufiicient amount of tetrakis- -(dimethylamino)ethylene to yield formulations containing 20, 30, 40 and 50 weight percent of the tetrakis compound. When these formulations are admixed with 'water, chemiluminescent smokes are produced.

EXAMPLE 3 Following the procedure of Example 1, equimolar amounts of triethyl aluminum and N,N, N, N'-tetramethyl ethylenediamine are prepared. To this mixture is added sufiicient amount of tetrakis(dimethylamino)ethylene to yield formulations containing 20, 30, 40 and 50 weight percent of the tetrakis compound. The resultant smoke formulation yields a chemiluminescent smoke when admixed with water.

Similarly, any of the chemiluminescent agents listed above can be used to replace the tetrakis compound to form a suitable chemiluminescent smoke formulation.

EXAMPLE 4 Following the procedure of Example 1, a smoke formulation is prepared in which dioxane replaces the hexamethylene tetramine complexing agent. A suitable chemiluminescent smoke formulation results.

Other typical ethers for use as complexing agents are tetrahydrofuran, diethyleneglycol dimethylether, diethyleneglycol diethylether, ethyleneglycol diethylether, and the like. Also, any form of the listed chemiluminescent agents suitable in Example 1 form suitable chemiluminescent smoke formulations.

EXAMPLE 5 Following the procedure of Example 1, equimolar amounts of diethylaluminum hydride and N,N,N'N'-tetramethylethylene diamine are prepared. To this mixture is added a sufficient amount of tetrakis(dibutylamino)ethylcue to form a chemiluminescent smoke formulation containing 20, 30, 40 and 50 weight percent of the tetrakis compound.

Typical chemiluminescent agents suitable for including in place of the tetrakis compound are listed above. Substiution of the chemiluminescent agents in the formulation of Example 5 produces satisfactory chemiluminescent smokes when contacted with water.

EXAMPLE 6 Following the procedure of Example 1, equimolar amounts of a mixture of 50 percent triethylaluminum-SO percent diethyl alumnum hydride and hexamethylene tetramine are prepared. To this is added a sufiicient quantity of the tetrakis(dimethylamino)ethylene to yield for- 1 1 mulations containing 20, 30, 40 and 50 weight percent of the tetrakis compound.

Suitable smoke formulations also result from substituting the chemiluminescent agents listed above for the tetrakis compound.

The smokes of this invention which are visible at night have many utilities. For example, they can be employed for marking purposes in sea rescues. Similarly, they may be used to direct artillery fire or aerial bombardments.

An important aspect of this invention is that the smokes are visible by day and at night. Hence, they have daytime and nighttime utilities. Accordingly, the compositions of this invention have a dual function. It is believed that this dual funtcion is not accomplished by smokes and flares presently in use. Moreover, the residue after dissemination by sublimation in water is a chemiluminescent film which floats on the surface of the water. This film is colored and typically orange. Since it is also visible in daylight, this aids in marking.

In addition, the chemiluminescent smokes of this invention produce sufi'icient light to illuminate the area in which the smoke is generated. The luminous flux, that is, the capacity of a chemiluminescent smoke to produce light measured in lumens, is relatively low in comparison with presently available flare materials. However, sufficient light is produced to enable one to make out the contours of terrain, for example. Moreover, the dual daylight-dark functionability of the smokes of this invention enable one material to perform the services of many presently used single-function materials.

Having fully described the novel compositions of this invention, their method of preparation and their utility, it is desired that the scope of this invention be solely limited by the lawful extent of the appended claims.

I claim:

1. A method for illuminating an area, said method comprising generating a chemiluminescent smoke in said area, wherein said chemiluminescent smoke is produced by contacting with water a chemiluminescent smoke agent consisting essentially of (a) an aluminum alkyl selected from trialkyl aluminum, dialkyl aluminum hydride, and mixtures of these, said aluminum alkyl having the formula: RR'R"Al wherein R and R are alkyl radicals of l-4 carbon atoms and R" is hydrogen or an alkyl radical of 1-4 carbon atoms, said aluminum alkyl being complexed with a chemically equivalent amount of (b) a complexing agent wherein said complexing agent is an alkyl amine having up to six carbon atoms or an ether having up to about 15 carbon atoms and 1-3 ether-oxygen linkages, said ether being free of acetylenic bonds, and admixed with (c) a chemiluminescent agent wherein said chemiluminescent agent is selected from the group consisting of (i) a tetrakis(di-lower alkylamino)ethylene, wherein said lower alkyl is a hydrocarbyl group having up to about 4 carbon atoms;

(ii) a hydrocarbyl-substituted nitrile, wherein said hydrocarbyl group is an alkyl, aryl, aralkyl, or akaryl group having up to about 16 carbon atoms;

(iii) a porphine selected from the group consisting of porphine, alkyl-substituted porphines, and metal chelate derivatives thereof wherein'said alkyl substituent has up to five carbon atoms, and said metal chelate derivatives are formed from metals selected from Groups I-B, II-A, II-B, III-A, and transition metals;

(iv) an indole selected from the group consisting of indole and hydrocarbyl-substituted indoles wherein said hydrocarbyl substituent is an alkyl, aryl, alkaryl, or aralkyl group having up to about 12 carbon atoms;

(v) a pyrrole selected from the group consisting of pyrrole and hydrocarbyl-substituted pyrroles wherein said hydrocarbyl substituent is an alkyl, aryl, aralkyl, or alkaryl group having up to about 12 carbon atoms;

(vi) a hydrocarbyl-substituted imidazole wherein said hydrocarbyl-substituent is an alkyl, aryl,

alkaryl or aralkyl group having up to about 12 carbon atoms; and

(vii) an acridine being selected from acridine and hydrocarbyl-substituted acridines wherein said hydrocarbyl substituent is an alkyl, aryl, alkaryl or aralkyl group having up to about 12 carbon atoms.

2. A method of claim 1 wherein said complexing agent is an amine selected from the group consisting of hexamethylene tetramine and N,N,N,N'-tetra(lower alkyl) ethylene diamine, said lower alkyl having up to about four carbon atoms.

3. A method of claim 2 wherein said chemiluminescent agent is a tetrakis(di-lower alkylamino)ethylene selected from tetrakis(dimethylamino)ethylene and tetrakis(dibutylamino)ethylene.

4. A method of claim 2 wherein said chemiluminescent agent is a nitrile selected from the group consisting of benzonitrile, propionitrile, and a-naphthonitrile.

5. A method of claim 2 wherein said chemiluminescent agent is a porphine selected from the group consisting of porphine, ZO-methylporphine, 4,14-dipentylporphine, 15- isobutylporphine, and said metal chelates of said porphines.

6. A method of claim 2 wherein said chemiluminescent agent is an indole selected from the group consisting of indole, 3-butylindole, 1,2-dimethylindole, 2-phenylindole, and 2,5-ditolylindole.

7. A method of claim 2 wherein said chemiluminescent agent is a pyrrole selected from the group consisting of 2,5-dipropyl pyrrole, Z-phenyl pyrrole, tetraethyl pyrrole, and l-isopropyl pyrrole. 1

8. A method of claim 2 wherein said chemiluminescent agent is an imidazole selected from the group consisting of 2,4,5-triphenyl imidazole, 2-benzimidazole, 2,5-dimethylimidazole, and 2-t olyl imidazole.

9. A methodof claim 2 wherein said chemiluminescent agent is an acridine selected from the group consisting of acridine, benz[c]acridine; 3 hexyl acridine, and S-tolyl acridine.

10. Method of claim 1 wherein said complexing agent is an ether having up to about 15 carbon atoms, from 1-3 ether-oxyen, linkages, and being free of acetylenic bonds.

11. A method of claim 10 wherein said chemiluminescent agent is a tetrakis(di-lower alkylamino)ethylene selected from tetrakis(dimethylamino)ethylene and tetrakis(dibutylamino)ethylene.

12. A method of claim 10 wherein said chemiluminescent agent is a nitrile selected from the group consisting of benzonitrile, propionitrile, and a-naphthonitrile. 13. A method of claim 10 wherein said chemiluminescent agent is a porphine selected from the group consisting of porphine, 20 methylporphine, 4,14-dipentylporphine, l5-isobutylporphine, and metal chelates of said porphines. g

14. A method of claim 10 wherein said chemiluminescent agent is an indole selected from the group consisting of indole, 3-butylindole, 1,2-dimethylindole, 2-phenylindole, and 2,5-ditolylindole. v

15. A method of claim lQ wherein said chemiluminescent agent is a pyrrole selected from the group consisting of 2,5-dipropyl pyrrole, 2-phenyl pyrrole, tetraethyl pyrrole, and l-isopropyl pyrrole. I 1

16. A method of claim 10 wherein said chemiluminescent agent is an imidazole selected from the group consisting of 2,4,5-triphenyl imidazole, 2-benzimidazole, 2,5-dimethylimidazole, and 2-tolyl imidazole.

17. A method of claim 10 wherein said chemiluminescent agent is an acridine selected from the group consisting of acridine, benz[c] acridine, 3-hexyl acridine, and 5- tolyl acridine.

18. A method of claim 1 wherein said area is a body of water and said method comprises release of said chemiluminescent smoke agent beneath the surface of said water.

19. A method of claim 1 wherein the aluminum alkyl is triethyl aluminum.

20. A method of claim 19 wherein said complexing agent is an ether selected from the group consisting of diethylether, tetrahydrofuran, and dioxane.

21. A method of claim 19 wherein said complexing agent is an amine selected from the group consisting of 22. A method of claim 21 wherein said complexing agent is hexamethylene tetramine, said chemiluminescent 'hexamethylene tetramine and N,N,N,'N-tetramethylethylene diamine.

agent is tetrakis(dimethylamino)ethylene, and said water is from an alum having the formula:

23. A method of claim 1 wherein the aluminum alkyl is a mixture of triethyl aluminum and diethyl aluminum hydride.

24. A method of claim 22 wherein said chemiluminescent agent is about 40 percent by weight of said chemiluminescent smoke.

25. A method of claim 19 wherein said complexing agent is tetrahydrofuran, said chemiluminescent agent is tetrakis(dimethylamino)ethylene, said water is from the atmosphere, said chemiluminescent agent being about 40 percent by weight of said chemiluminescent smoke agent, and said contacting is carried out by exposure of said chemiluminescent smoke agent to the atmosphere.

References Cited UNITED STATESPATENTS 3,309,268 3/1967 Sherman 252305 JOHN D. WELSH, Primary Examiner US. Cl. X.R. 252-305; 149--l09 

